Surface active rosin derivatives



Patented May 22, 1945 SURFACE AC T IVEROSIN DERIVATIVES Donald Price. New York, N. Y., and Everette L. 1 May, East Orange, N. J., assignors to National Oil Products Company, Harrison, N. J a corpov ration of New Jersey No Drawing. Application September 13, 1941,

. Serial No. 410,778

11 Claims This invention relates to derivatives of rosin and allied compounds, and more particularly to novel sulfonated derivatives having excellent surface active propertiesand to correlated improvements. in the preparation of such products. The subject matter of the present invention is closely related to that of the copending application of Price and May, Serial No. 410,779, filed concurrently herewith and entitled "Rosin derivatives, wherein certain alkyla'te'd rosin derivatives and the summation products thereof are disclosed and claimed.

Rosin and allied materials afford a cheap source of uniform and reactive organic raw material, and numerous products are, at the present time, manufactured from these substances. However, there have not heretofore been developed any rosin products, other than the rosin soaps, 'pos-, sessing in any substantial degree the properties of detergency, wetting power and foaming power. It is accordingly an object of this invention to provide novel derivatives of rosin and allied substances which will possess these properties.

This object and others have been achieved by this invention in products which are formed by the sulfonation and alkylation of rosin and like substances. Preferably, each molecule of the product/will contain one sulfonic group and one alkyl group of substantial length, but each rosin molecule may contain two or more of either or both of these groups. The products may be made by sulfonating the rosin compound and, thereafter alkyiating; or both reactions may be carried out concurrently. The present invention is confined, to rosin compounds alkylated in the presence of a strong sulfonating agent, other analogous compounds being covered in the aforesaid application of Price and May. l

Rosin has been cited hereinabove as an example of a raw material for the manufacture ofproducts according to this invention. However, in-- stead of rosin, hydrogenated, dehydrogenated, disproportionated or decarboxylated rosin, or rosin oils may be employed. Likewise suitable are the rosin acids corresponding to the foregoing compounds, such as, for example, abietic, pimaric, sapinic and the like acids. Similarly, the glyceryl, glycol, ethylene glycol, diethylene glycol, methyl, ethyl, propyl, butyl, pentaerythri- 1:01 and other esters of rosin or rosin acids, or of hydrogenated, dehydrogenated or disproportionated rosin or rosin acids may be employed. Examples of these are hydrogenated, dehydrogenated and disproportionated ester gum; the' glyceryl, glycol, ethylene glycol, diethylene glycol.

methyl, ethyl, propyl, butyi, pentaerythritol'and like esters of abietic, dihydroabietic and dehydroabietic acids. allied substances will be termed generically in this specification and the appended claims as rosin compounds Coming now to the alkylation of the rosin compounds which may optionally have been sulfonated beforehand, the alkyl group to be combined with the rosin substance mayv be any alkyl or aralkyl group containing upwards of 8, and preferably between 10 and 14, carbon atoms. Such groups may be furnished as alcohols, alkenes or naphthenes, and may be condensed with the rosin material by means of any appropriate strong sulfonating agent, such as sulfuric acid, oleum or chlorsulfonic acid. The, temperature at which the condensation is carried out may vary from about 20 C. to 50" C. and the reaction will be completed in about 2 to 6 hours, usually between about 2 and 4 hours.

Suitable alcohols for furnishing the alkyl constituent include alcohols containing 81 or, more, and preferably from 10 to 14, carbon atoms, such as octyi, nonyl, decyl, undecyl, lauryl,'myristyl, and the like alcohols; or any mixture of alcohols meeting the above requirements, such as the mixed alcohols derived by hydrogenation of the fatty residues of various oils such as coconut oil, babassu oil, soybean oil and the like. Suitable alkenes maybe derived by any conventional process, such as the dehydration of the above alcohols or may be obtained from petroleum products containing-unsaturated aliphatic compounds of 8 or more, preferably 10 to 14,-carbon atoms.

The sulfonation of rosin products contemplated by this invention will usually take place during the condensation of the alkyl constituent with'the rosin compound, the sulfuric acid or other sulfury] condensing agent acting as a sulfonating agent. However, in some cases the conditions of alkylation may be such that the desired degree of sulfonation does not take place during that usual sulfonating agent, such as sulfuric acid,,

oleum, sulfur trioxide,,chlorsulfonic acid and the like. This reaction may conveniently be carried out by slowly mixing oleum with the alkylated or unalkylated rosin material, dissolvedyif desired;*

in an inert solvent, and maintaining the mixture at room or only slightly elevated temperature for from about 'to about 3 hours, after which the,

mixture is neutralized and the sulfonated product Hereinafter all the foregoing and is isolated, if desired. by extracting it by. means of suitable solvents from the neutralized mass. 4

Products prepared as above outlined are all readily soluble in water to form solutions which *have excellent detergent and foaming properties and exert powerful wetting and penetrating actions. They are further highly resistant'to hardness, acidity, and alkalinity in the media in which they are employed. These properties adapt the products to many industrial and domestic uses.

such as scouring. leveling, dye penetrating and i introi'ying. laundering, cleaning of various solid surfaces, removal of spray residues from iruit and produce, formation of emulsions for spraying. waxin etc., stabilization of latex and many other uses of a like nature.

With the above general discussion in mind, there are set forth below specific examples of the manufacture of products according to this'invena tion, which examples are to be considered merely as illustrative, and not in any limiting sense. All parts given are by weight. v

Example I 10 parts '(1 mol) of rosin and B parts (1 mol) of lauryl alcohol were mixed and warmed on a water bath until a homogeneous mixture was obtained. The mixture was cooled to 20 C. and 14 parts of 20% oleum were added slowly with stirring attemperatures maintained between 20 C. and 30 C. The reaction was completed by stirring at room temperature for 3 hours, after which the mass was poured into 45 parts of 30 B.

The neutralized mass was evaporated to dryness. The

NaOH and the 'pH was adjusted to 8.5.

resulting product, which contained monolauryl rosin monosulfonate as the active ingredient, was an efllcient detergent characterized by strong.

foaming, wetting and penetrating powers.

Example II .10 parts (1 mol) of rosin and 6 parts (1 mol) of the alcohols derived by the reduction of 6060-, nut oil fatty acids were mixed and warmed on a water bath until a homogeneous mixture was obtained. The mixture was cooled to 20 C. and 14 parts of 20% oleum were added gradually mixture was cooled to 20 C. and 14 parts of 20% oleum were added gradually with stirring at temperatures maintained between 20 C. and 30 C. The reaction was completed by stirring at room temperature for 3 hours, after which the mass was poured into 45 parts of 30 B. NaOH and the pH was adjusted to 8.5. The neutralized mass was evaporated to dryness. The product exhibited excellent wetting-and d'etergent properties.

. Eaample V 10 parts (1 I (Galex" manufactured by the National Rosin Oiland Size Co. of Savannah, Georgia) and 12 parts (2 mols) of the alcohols derived by the reduction of coconut oil fatty acids were mixed with stirring at temperatures maintained between 20 C. and 30 C. The reaction was completed by stirring at room temperature for 3 hours, after which the mass was poured into 45 parts of 30 B. NaOH and .the pH was adjusted to 8.5. Thelneutralized mass was evaporated to dryness. The product exhibited excellent wetting and. detergent properties.

Example III was increased to 18 parts. An excellent surface 10 parts (1 mol) of rosin and 5'" parts (1 mol) I exhibited excellent wetting and detergent prop-v ertie's. Example IV parts (1 mol) ofrosin, 'l'parts (1 mol) of I -myristyl alcohol and '7 parts of ethylene dichlo ride were mixed and warmed on a water bath ous mixture was obtained. The mixture was cooled to C. and 18 parts o: 20% oleum were added slowly with stirring at temperatures maintained between 20 C. and C. The reaction was completed by stirring at room temperature for 3 hours, after which theanass was poured into 60 parts of B. NaOH and the pH was adjusted to 8.5. The neutralized mass was evaporated to dryness. The product, the active incredients oi whichwere sulfonateddehydroabietic acids largely dialkylated with the coconut oil fatty residues, exhibited excellent detergent powers.

Example VI Abietic acid was substituted for the Galex in the procedure of Example V. The product was an excellent detergent and wetting agent. I

Example VII loparts (1 mol) of ester gum and 8 parts (1 mol) of coconut fatty alcohols were warmed, mixed and'cooled to 25 C. 14 parts of 20% oleum were added slowly with stirring. Stirring was continued at room'temperature for 3 hours. Thereafter the mass was poured into parts of 30 B. NaOH and the pH adjusted to 7.5. The neutralized mass was extracted with butanol and dition- This product was freely soluble in water.

, Example VIII The procedure of Example was followed,

an excellent detergent,

except that the quantity of coconut fatty alcohols was increased to 12 parts (2 mols) and the oleum active agent resulted.

, Example IX 10 parts (1 mol) of rosin oil and 6 parts (1 mol) I of coconut fatty alcohols were warmed, mixed and cooled to 20 C. 18 parts of 20% oleum were added with stirring, the temperature being main-- tained between 15 C. and 25 C. Stirring was continued at room temperature for 3 hours. Thereafter the mass was poured into parts of 30 NaOH and the pH adjusted to 7.5. The mass was evaporated to dryness, leaving a sulfonated product having the same excellent properties characteristic of the other products afore- )1 mentioned.

Example X 6 parts (1 mol) of the trihydrate of dehydroabietic acid sulfonate (Ga-lex sulfonic acid) and 5.5 parts (2 mols) of the alcohols derived by the reduction of coconut oil fatty acids were mixed until a homogeneous mixture was obtained. The 1 and 11 parts of 20% oleum were added with stirmen or dehydroabietic acid.

' and warmed on a water bath untila homogene- I "the butanol distilled oil from the extract solution to leave the sulfonated product insalt-free conlike salts thereof.

ring over a period of 30 minutes while maintaining thetemperature between 30 and 35 C. The mass was maintained at 35 C. while stirring for three and one-half hours and then neutralized by pouring the same into 35 parts of 30 Be. soda and adjusting the pH to 7.5 to 8.0. The water was evaporated from the mass under reduced pressure yielding 25 parts of a light-colored solid (40% active) having excellent detergent properties.

.It will thus be seen that there is provided by this invention a class of surface active compounds which may be easily and cheaply prepared from readily and cheaply procurable starting materials. These products are all characterized by outstanding detergent, wetting and foaming powers and by their retention of these powers in spite of the acidity, alkalinity and hardness of the media in which they are used.

r The expression sulfonated is used herein to connote both the sulfonic acid derivatives as well as the corresponding alkali metal, ammonium and Since certain changes in carrying out the above process and certain modifications in the product which embody the invention may be made without departing from its'scope, it is intended that all matter contained in the above description shall be interpreted as illustrative and not in a limitin It is also to be'understood that the following claims are intended to cover all the generic and specific features of the invention herein "described, and all statements ofthe scope of the invention, which as a matter of language might be said to fall therebetween. I 7

Having described our invention, what we claim as new and desire to secure by Letters Patent is:

1. A process of producing novel surface active compounds which comprises reacting a compound selected from the group consisting of rosin; hydrogenated, dehydrogenated, disproportionated and decarboxylated rosin; th free acids corresponding to rosin and hydrogenated, dehydrogenated and disproportionated rosin; and esters of the aforementioned acids; with a strong sulfonating agent and a compound selected from the roup consisting of aliphatic alcohols and alkenes having at least eight carbon atoms.

2. A process of producing novel surface active I compounds which comprises reacting a compound selected. from the group consisting of rosin;

hydrogenated, dehydrogenated, disproportionated 4. A process of producing novel surface active compounds which comprises reacting rosin oil with a strong sulfonating agent and a compound selected from the group consisting of aliphatic alcohols and alkenes having ten to fourteen carbon atoms.

5. A process of producing novel surface active compounds whichcomprises reacting dehydroabietic acid with a strong sulfonating agent and a compound selected from the group consisting of aliphatic alcohols and alkencs having ten to fourteen carbon atoms. 7

6. .A process of producing novel surface active compounds which comprises reacting a compound selected from the group consisting of rosin; hydrogenated. dehydrogenated, disproportionated and decarboxylated rosin; the free acids corresponding to rosin and hydrogenated, dehydrogenated and disproportionated rosin; and esters of the aforementioned acids; with a strong sulfonating agent and an aliphatic alcohol contain v ing ten to fourteen carbon atoms.

7. A process of producing novel surface active compounds which comprises reacting a compound selected from the group consisting of rosin:

hydrogenated,- dehydrogenated, disproportionated and decarboxylated rosin; the free acids'corresponding to rosin and hydrogenated, dehydrogenated and disproportionated rosin; and esters of the aforementioned acids; with a strong sulfonatin'g agent and an alkene containing ten to fourteen carbon atoms.

8. The sulfonated product of the treatment of a mixture of a compound selected from the group consisting of rosin; hydrogenated, dehydrogenated, disproportionatedand decarboxylated rosin;

the free acids corresponding to rosin and hydrogenated, dehydrogenated and disproportionated rosin: and esters of the aforementioned acidsr and decarboxylaited rosin; the free acids corresponding to rosin and hydrogenated, dehydrogenated and 'disproportionated rosin; and esters of the aforementioned acids; with a strong sulfonating agent and a compound selected from the group consisting of aliphatic alcohols and alkenes having ten to fourteen carbon atoms.

3. A process of producing 'novel surface active compounds which comprises reacting rosin with a strong sulfonati'ng agent and a compound selected from the group consisting of aliphatic alcchols and alkenes having ten to fourteen carbon atoms.

and lauryl alcohol with a strong sulfonating.

agent.

9. The sulfonated product of the treatment of a mixture of a compound selected from the group consisting of rosin; hydrogenated, dehydrogenated, disproportionated and-decarboxyiated rosin; the free acids corresponding to rosin and hi drogenated, dehydrogenated and disproportionated rosin; and esters of the aforementioned acids; and myristyl alcohol with a strong sulfonating agent.

10. The sulfonated product of the treatment of a mixture of a compound selected from. the group 1 consisting of rosin; hydrogenated, dehydrogenated, disproportionated and decarboxylated rosin? I the free acids corresponding to rosin and hydroa genated, dehydrogenated and disproportionated rosin; and esters of the aforementioned acids; and cocoanut fatty alcohols with a strong sulfonating agent.

I 11. The sulfonated product of the treatment of a mixture of dehydroabietic acid and cocoanut fatty alcohols with a strong sulfonatingagent.

DONALD PRICE.

' EVERETTE L. MAY. 

